Optically supersensitized photographic silver halide emulsion



Patented Sept. 7, 1948 OPTICALLY SUPERSENSITIZF.ILD-PI-lllO-'IO-A i GRAPHIC SILVER EMULSIQN..

Burt H; Carroll-and Cyril J". Stand, Rochester,

N. Y., assignors to Eastman KodaknCompany, Y Rochester, N. Y., a corporationiof` New.l'ersey.

Application November 23, 1945, Serial. No. 630,544.

19 Claims.

This invention relates to sensitized photographic emulsions and toa process for-the preparation thereof.

It is known that photographic silver halide emulsions can `bezspectrally (optically) sensitized with certain dyes` whichA adsorbdirectly on the silver halide. It is also known that acid and basic sensitizing dyes are relatively incompatible; for example, sensitization lby means vof com.- Ibinationsof eosin dyes. land cyanine dyes is genera/113,11'.weakerv thanlthe sumof the individual eects producedby eosin dyes (acid) and the cyanine dyes .(basic);

We have nowk found' thatcertain dyes of the oxonol series many of which, in and ofthemselves, have only a Weak sensitizing'action (or even. noa'pprecia'ble sensitizing. action) on photographic silver halide emulsions, and are only slightly adsorbed (or not appreciably adsorbed) on the silver halide, will' sensitize, or show greatly improved sensitization of,` photographic silver halidev emulsions in the presencev of one or more monomethine cyanine dyes (or salts), trimethine cyanine dyes. (or salts), dimethine hemicyanine dyes (or salts) or styryl dyes (or salts).

The spectral sensitivity conferred on emulsions by the oxonol dyes, in accordance with our invention, disappearsl completely duringdevelopmentv ofthe emulsionsin' ordinary developers contain-1 ing-a,4- sulilt'e; such asV sodium sulte, althoughl moderately lstrong values of `red and. green-sensitivity can be obtainedduring'exposure. Thisloss of optical sensitivity during'- developmentJ isunlike thesituati'on whichA obtains when Va l sensitiz ingvdye is adsorbed directly onfthe silver halide, as is the case in emulsions spectrally. sensitized with cyani'ne'dyes alone. Because the-spectral sensitivity conferred uponv thel emulsions, by the oxonol dyes; in accordancewith our invention, is lost during development, the invention is particularlyuseful yin--connection with certain color phothe red sensitization introduced into the hluefsensitive layer persists through-the-'first'development of the selective" reversalprocess, cyan is introduced into all yellows, with less satisfactory results than is the case when the excessive-yellow.

is not corrected. Our'i'nventionprovides a means...A of arriving at the desired red sensitiv-ity whichfis.-

then removed during the iirstdevelopment.`

` Our invention is also very useful for the sensi-- tization of photographic silver halide emi-listens-y Which are used' under circumstances wherefstaining caused by residual sensitizing dye is undesirable, as in the case of emulsions used'to prep-are photographic printing lpaper or tov prepareV iilm for ,photomeohanical reproduction. Since thef acid oxonol dyesk which we Ause in practicing-v our invention are removed during development; the.A

dyes do notV stain the developed element.

It kis, accordingly, an object of our invention to provide novel', sensitized photographic emu-lsions and to provide a process for the -prcparationr thereof. hereinafter;

l In vaccordancewith our invention, we incorporate' in a photographic silver halide emulsion at least one pentamethineI oxonolV dye selected fromthose represented by the following general formula:

/Z\` l/Z'x` o=6--;='LL=L-L=L-6 `ooH wherein L represents a methine group substituted or unsubstituted and Zr and Z eachrepresents the non-metallic atoms necessary to. completea heterocyclic nucleus containing from 5 to 6v atoms. in the heterocyclic ring or the metal or ammonium (substituted or unsubstituted) salt forms of these dyes. and also incorporate in said emulsion as a supersensitizer for the sal-d pentamethine oxonoldye, at least one basic dye selected from the group consisting of monomethine cyanine dyes, trimethine cyanine dyes, dimethine hemicyanine dyes and styryl dyes. The pentamethine oxonol dyeswherein Z'or Z represents .the nonmetallic atoms necessary. to completea 5,-pyrazolonenucleus containing a carboxyl group and/ or a sulfo group, e. g., a 3-carboXy-5-pyrazolone nucleus, a 1-sulfophenyl-S-carboxy-E-pyrazolone nucleus, a 1-sulfophenyl-3-methyl-5-pyrazolone nucleus, a 1-(2,5-dichloro 4 sulophenyl) -3- Other' objectswil-l5l become apparent.vr

i halide emusions.

or sulfo group or the ammonium or metal salt forms of such groups.

We are aware of the fact that symmetrical oxonol dyes of the above formula have been employed as filter dyes. However, we do not employ the dyes in concentrations great enough to produce any practical filter action. As pointed out in British Patent 506,385, dated May 24, 1939,

when the oxonol dyes are used as filter dyes, they i are employed in such an amount that, with respect to colored light for which the dye has its predominant absorption, the optical density of:

the material is greater than one. Gontrasted with y this, We employ the oxonol dyes in practicing our invention, in a concentration of not more than 0.2" gram per gram-mole of ,silver halidein thel emulsion. Usually We employ the oxonol'dye in a concentration of from about 0.025 to about 0.15 gram of dye per gram-mole of silver halide in the emulsion. l r.

,i The quantity of basic dyeemployed may be several times greater than the concentration of the oxonol dye. Generally speaking, the most useful concentration of the basic dye is from 2 to 3 times the concentration of the oxonol dye, although higher or lower concentrations can be used, e.- g., equal concentrations. The most effective concentration of the basic dye will be apparent in any given instance rupon making the usual tests and yobservations customarily employed in the art. r

As pointedout above, the basic dye may,.in andlof itself, have a sensitizing action upon the photographic emulsion, but this is .not necessary. 4Among rthe monomethine cyanine, trimethine cyanine, dimethine hemicyanine and styryl dyes which are most useful in practicingour invention are those-which confer, in and of themselves no appreciable red sensitivity on photographic silver Such .dyes act .to supersensitize the pentamethine oxonol dyes, thereby 1 conferring, in addition, red sensitivity on the y (Pi (J) 3,3,9trialkyl6,7-benzoxathiacarbocyaninc salts, c. g.

3,3-diethyl-9methyl6,7-benzoxathiacarbocyanine bromide 2-(p-dxmethylaminostyryl)pyridine ethiodide 2(pdialkylaminostyryl)benzothiazole alkyl e. g. l v

2-(p-dimetliylaminostyryl)benzoselenazolc ethicdide (Z) 2-(p-dialkylamiuostyryl)quinoline alkyl-Quaternary salts, e.r g..

In al1 of the above groups of basic dyes those in. which .the alkyll groups contain from 1 to 4; carbon atoms are advantageously employed and those in which the alkylgroups are ofthe formula CdHzd+i whereiny d represents a ypositiveinteger be added rst'or the substances may be added l to the emulsion together. One or more off-the oxonol dyes can be employed and one or more of the basic dyes canbev employed. I

. The following examples ,will serve to illustrate further the manner of practicingour invention.

Exemple 1 Bis[1-p-su1fophenyl-3-methyl-- 5 pyrazoloriefl l(4)]pentamethine oxonol, in concentrations oi 0,043 'to 0.21g. permole of. silverhalide, caused 2-(p-dalkylaminostyry1)pyridine alkyl quaternary salts, .e.A g.. Quaternary salts,A

2-(p-dialkylaminostyryl)--naphthotliiazole alkyl Quaternary' 2-(p-dialkylaminostyryl )benzo'selenazole alkyl-Quaternary salts;-

audace barely detectable red sensitization in a fast negati'vetytie-ofl 'gelatino-silver-bromiodide emulsion. Moderately good red sensitization with maximum at about' 680 mu wasv produced by the aforesaid oxonol dye, in a concentration of 0.043 g. per mole of'siiver halide, in the aforesaid emulsion in the presence of the following basic dyes:

Basic Dye Cmgtra 3-methyl-l'-ethylthiacyanine iodide 3,3*-diethyloxacarbocyanine iodide. 3,3diethylenethiacyanine iorilde... l 2-[-(l-piperidyDvinyll-benzothiazole methochloride..

Example 2 Bisil phenyl-S-methyl 5 pyrazolone-(e) lpentamethine oxonol, in concentration of 0.087 g. per mole of silver halide, caused very weak red sensitization in'a fast negative type of gelatinoysilver-halide emulsion with a maximum at about 670 mu. Much stronger red sensitization was produced in the same region by the aforesaid oxonol dye' in the aforesaid concentrationy in the aforesaid-emulsion, in the presence of the following basic dyes:

Concentration, g. per Red Speed Basic Dye mole of silver Increase halide N,Nethylenethiacyanine iodide (8,3- 0. 087 25 fold.

ethylenethiacyanine iodide). Z-I-(l-piperid )viny1] -naphtho 0.087 10 fold.

thiazole ethiodide. 1-(Ibenzothiazo1yl)4[3 -ethyl -l(2) 0.087 l0 fold.

b e n zoxazolylidene) ethylidcne] 3 methyl--pyrazolcne.

None of the above basic dyes is capable of producing red sensitivity in and of itself.

Example 3 Bis-[1,3 diethylbarbituric acid (5)] pentamethirie oxonol, in a concentration of 0.085 g. per mole of-silver halide, caused very weak red sensitization in a process gelatino-silver-bromiodide emulsion. Much stronger red sensitization was produced in the same region by the aforesaid oxonol dye in the aforesaid concentration inv the same emulsion, in the presence of 3,3- ethylenethiacyanine iodide (0.085 g. per mole oi silver halide) Similarly bis[3 carboxy 5 pyrazolone (4) pentamethineleoxonol and `bis[3emethyl-5-py- Iazolone-(4)l-pentamethine oxonol, neither of which gives any measurable red sensitivity .in lgelatino-silver-halide emulsions alone, each gave some red sensitivity, in the presence` of N,N ethylenecyanine iodide or chloride.

Ina manner similar to that illustrated in the foregoing examples photographic silver halide emulsioncan be sensitized with other supersen sitizing combinations of pentamethine oxonol dyes-andbasic dyes.

The accompanying drawing illustrates graphically the supersensitizing effect obtained with two of our new combinations in a 'gelatine-silverbromoiodide emulsion. Each figure in the drawingV is a diagrammatic reproduction ofthree spectrogra-ms. In Fig. l, curve A represents the sensitivity of a gelatine-silverebromoiodide"emulsion containing bis l-phenyl-3methyl5epyrazolone- (4) lr-pentamethine oxonol ina concentration'` of 0-.08'7 g. per mole of silver nali-dein theemulsion.v The same curve also represents the sensitivity of the same emulsion containing 3,3"ethylenethiacyanine iodide in a concentration of 0.087' g; per mole of silver halide in the emulsion. Actually the curve representstthe spectral sensitivity of the emulsion. without either of the above compounds, sin-ce at the concentrations indicated;y neither compound, alone, y confers any-appreciable extra spectral sensitivity on t'h'e emulsion. Curve B represents the sensitivity of the same emulsion containing both of the aforesaid 'dyes in thel concentrations set forth above. The emulsion nowpossesses substantial red sensitivity along ivi-thits inherent blue sensitivity, Whereas before, it possessed no appreciablered sensitivity.

In Fig. 2, curve C represents the sensitivity of a gelatino-silver-bromiodide emulsion containing bisll phenyl-3 1nethyl5pyrazolone(4) lenen-- tamethine oxonol in a concentration of 0.87- g. per mole of silver halide in the emulsion. They same curve also represents the sensitivity of the same emulsion containing V2-i'- (1-piperidyl)vinyl'l` naphth'othiazole ethiodide in a concentrationv of= 0.87g. per mole of silver halide in the emulsion'. Actually the curve representsfthe spectral sensitivity of the emulsion Without either' oi the aforesaid dyes, since at the concentrations indicated, neither dye, alone, confers any appreciable extra sensitivity on the emulsion. Curve vD represents the sensitivity of the same emulsion containing both of the aforesaiddyes in the concentrations set forth above. The emulsion now possesses substantial red sensitivity along with 4its inherent blue sensitivity, whereas before, it possessed :no appreciable red sensitivity.

The pentamethine` oxonol dyes can be incorporated in the emulsions directly or in the form'l of a solution in a suitable solvent, e. g. methyl alcohol, ethyl alcohol or acetone. The oxonol dyes including. those containing a carboxyl and/ or sulfo group, can also be employed in the form of their metal 0r ammonium salts. The saltsy are advantageously formed by adding to the oxonol dye, Wet with a little water, methanol or ethanol, an alkali metal hydroxide, e. g. sodium or potassium hydroxide, or ammonium hydroxide, or an amine, e. g. methyla-rnine, ethylamine,I dimethyli amine, diethylamine, trimethylamine, triethylamine, ethanolamine, diet'hanolamine, triethanole amine, pyridine, Nemethylpiperidine, n-propylamine, isopropylamine, butylamine, --ethoxyethyl-e amine, etc., andV taking. up the salt Which forms" in a suitable solvent, e. g. water, methanol, ethanol, armixture of Water and methanol or a mixture of Water and ethanol.

The basic dyes can be added to the emulsions directly or in the form of a solution in a suit-` able solvent, e. g. methanol, or ethanol.

The pentamethine oxonol dyes and the basic dyes are advantageously added to the Washed, nished emulsions and should'be'uniformly distributed throughout the emulsions.

Our' invention is directed primarily' to the customarily vemployed gelatino-silVer-halide developing-out emulsions, such asgelatinoesilver-chl'oride, gelatine-silver-chlorobromide, gelati'm'i-sil-v ver-iodochloride,l gelatino-silver-chlorobromi dide, gelatino-silver-bromide and gelatine-silverbromiodide emulsions.

Cyanine dyes, hemicyanine dyes and styryl dyes are defined in The Theory of .the Photographic Process, C. E. Kenneth Mees, The MacMillan Company, New York, 1942.

Emulsions prepared in accordance with our invention can be coated in the' usual manner on any suitable support, such as glass, cellulose acetate lm, cellulose nitrate film, polyvinyl acetal resin lm, paper or a suitable metal support.

3,3'ethylenethiacyanine salts and 3,3et'hyl ene-oxacyanine salts are described in the copending application of Leslie G. S. Brooker and Robert H. Sprague, Serial No. 563,086, filed November 11 ,1944, as are other N,Nethylenecyanine salts;

Pentamethine oxonol dyes can ybe prepared by condensing glutaconic aldehyde dianilide hydro-- chloride with one or more ketomethylene -compounds selected from those represented by the following general formula:

v O=-H7 wherein Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from to 6 Iatoms in the heterocyclic ring, e. g. 3-methyl-l-phenyl-5-pyrazolone, B-methyl- 1-sulfophenyl5-pyrazol-one, thiobarbiturio acid, barbituric acid, etc. Two moles of the keto-` methylene ycompound per mole of the glutaconic aldehyde dianilide hydrochloride are ladvantageously employed. The condensations are advantageously eected either in pyridine or in an ethyl alcoholic solution of a strong base such as triethylamine. The condensations can be accelerated by heating on a water or steam bath.

What we claim as our invention and desire to be secured by Letters Patent of the United States' 1s: p 1. A photographic silver halide emulsion sen-` sitized with a supersensitizing combination of at least one oxonol dye selected from the group con` sisting of those represented by the following general formula:

wherein L represents a methine group and Z and Zveach represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, and the metal and ammonium salt `forms of the formulated dyes, in a, concentration of not more` than 0.25 gram per mole of silver halide in the emulsion, and, as a supersensitizer for the oxonol dye, at least one basic dye selected from the group consisting of monomethine cyanine dyes, trimethine cyanine dyes, dimethine hemicyanine dyes and styryl'dyes.

` 2. A photographic silver halide developing-out emulsion sensitized with a supersensitizing combination of at least one oxonol dye selected from` ring,'andv the alkali metaland ammoniumfsaltf forms ofthe formulated dyes, in a concentration `of not more than 0.25 gram per mole-ofA silver' halide in the emulsion, and, as a supersensitizer for the oxonol dye, at -least one basic dye selectedfrom the group consisting of monomethine cyaex nine dyes, trimethine cyanine dyes, dimethine; 'hemicyanine dyes and styryl dyes.

3. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one oXonol dye selected from the group represented by the fOl-f lowing generalv formula:

wherein L represents a methine group and Zand- Z each represents the non-metallic atomsr'necessary to complete a heterocyclic nucleus contain# ing from 5 to 6 atoms in the heterocyclic ring and the metal and ammonium salt forrnsof` the' wherein Z and Z each represents 'the non'- metallic atoms necessary to complete a heterocyc=lic nucleus containing from 5 to 6 atoms in the heterocyclic ring and containing a member selected from the group consisting of sulfo groups, carboxyl groups and the ammonium and alkali metal salt forms of said groups, in aconcentration 0f not more than 0.25 gram per mole of silver halide in t-he emulsion, and,v as a supersensitizer for the pentamethine oxonol dye, at least one basic dye selected from the group-consisting of monomethine cyanine, trimethine cyanine, dimethine hemicyanine. dyes and-` styryl dyes. 5. A photographic gelatino-silver-halide developing-out emulsion sensitized with' a supersensitizing combination of at least one pentamethine oxonol dye selected fromv the group represented by the following general formula; l.

/ZX /Z'\ i v o= e o-OH wherein Z and Z' each represents thefjnor'ifv metallic atoms necessary to complete ya hetero? cyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring and containing a member selected from the group consistinglof sulio groups, carboxyl groups and the ammonium and alkali metal forms of said groups, vin a concentration of' not more than 0.25 gram per mole o f silver halide in the emulsion, and, as a supersensitizer for the pentamethine oxonol dye, at least one basic ydye selected from the group consisting ofr monomethine cyanine dyes, trimethine cyanine dyes, dimethine helnicyanine dyes and styryl dyes.

6. A photograph silver halide vdevdopingout emulsion sensitized with a supersensitizing cornbination lof at least vone pyrazolone p'entamethine' Concentra- Basc Dye non 3.rnethyl'lethylthiacyanine -iod ide 3jSJdiethyloxacarbocyanine iodide. 3,3diethylenethiacyanine iodide 2[(1-pperidyl) vinyl1-benzothiezole methochloride..

None of the above basic dyes are capable of produoingred sensitivity, in and of themselves.

Upon development, with or Without exposure to white light, for 4 minutes in Eastman Kodak Companys -D-19 developer, the red sensitivity produced according to Aany of the foregoing embodiments `disappeared practically completely, uthe developed-emulsion lbeing no more sensitive .tored light than was the originalemulsion which `did not-containfthefoxonol 'dye'or the basic dyes.

Eample 2 Bis[1 phenyl-S-methyl 5 --pyrazolone-(li) vllpentamethine oxonol, in concentration of 0.087 g, `peru-mole of silver halide, caused very weak red .sensitization in a fast negative type `of gelatineysl1-verha1ide emulsion with a maximum at about 670 mu. Much stronger red sensitization was produced in the same region by the aforesaid oxonol dye .in the aforesaid concentration in the aforesaid-emulsion, inthe presence ofthe following basic dyes:

@None/of the labove basic dyes is capable of'produoing red sensitivity in and of itself.

Example 3 '=Bisi[.1,3 -fdiethylbarbituric lacid (5)] pentamethin-e loxonol, in a concentration yof 0.085 g. per moleof lsilver "halide, caused very Weak -red sensitization in a process gelatino-silver-bromiodlde emulsion. Much stronger red sensitization was produced in the same region by the aforesaid oxonol dye inthe aforesaid concentration inthe same emulsion, in the presence of 3,3- vethylenethiacyanine iodide (0.085 g. per mole of silver halide).

Similarly bis ['3 carboxy '5 pyrazolone (4) gpentamethinel-oxonol and bis[3-methyl-'5-py .razolone-(4')lfpentamethine oxonol, neither of which gives any measurable red sensitivity in vgelatino-silver-halide emulsions alone, each gave some red sensitivity, in the presence of lN,l\T ethylenecyanine iodide or chloride.

In a manner similar to that illustrated in the 'foregoing examples photographic silver halide emulsion can-be sensitized with other supersensitizing combinations of pentamethine oxonol dyesand basic dyes.

The accompanying drawing illustrates graphiper mole of. silver halide in the emulsion.

centrations set .forth above.

6 cally the-'supersensitizing `elect obtained lwith two o1" our Inew combinations in a gelatino-'silver bromoiodide emulsion. Eachfgurein"thefdrawing isa diagrammatic:reproductionfofthree spectrograms. lin-Fig. 1, curve Aarepresentsithe-sensitivity of a gelatino-silver-brornoiodide emulsion containing bis 1-pheny1-3 -methyli -pyrazo'lone-` (4") l-.pen'tamethine oxonol in v:a:concentration of l0.087 g. rp'er mole. oi silver *halide y'in the-emulsion. The same curve also represents the--sensitivity ofthe same emulsion containing 3,3v-'ethylenethiacyanine iodide inra concentration fo'f Jrl)087=g.

Actually the curve represents 'the spectral sensitivity of the emulsion Without either of the above oompounds, since at the concentrations indicated.

neither compound, alone, con'fersany appreciable extra spectral sensitivity onth'e emulsion. IlCurve -Brepresents the sensitivity of the same emulsion containing both ofthe vaforesaid ldyes yin the con- The emulsion'fnow possesses substantial red sensitivityfalongwithfits inherent blue sensitivity, Whereas before, it possessed no appreciable red sensitivity.

In Fig. 2, curve C represents the sensitivity of a gelatino-silver-bromi'odide emulsiony containing bis [1 .phenyl-3-rmethyl--pyrazolon'e-f (4) l--pentamethine oxon'ol in 'a concentrationiof 02'8'7ig. per mole of silver halide y:in 'the emulsion. 'The same curve 'also represents the sensitivity of 'the 'same emulsion containing .-2- l-piperidyl-f) vinyll--- naphthothiazole `etlfiiodide in a :concentration vo'f 0.87 4rg. per mole of* silverhalide in :the emulsion. Actuallythe curve yrepresents the spectral :sensitivity'of theaemuls'ion'without'either of theaforesaid "dyes, since at the concentrations indicated,

neither'dya alone, confers yany 'appreciable extra sensitivity onzthe emulsion. Curve ID represents the sensitivity of lthe same emulsion ycontaining both of the aforesaid dyes in the concentrations dyes includingthose containing a carboxylv and/ or sulfo group, can also be employed in the form of their metal or ammonium salts. The salts are advantageously formed by adding to the oxonol dye, Wet with a little Water, methanol or ethanol, an alkali metal hydroxide, e. g. sodium or potassium hydroxide, or ammonium hydroxide, bran amine, e. g. methylamine, e'thylamine, dimethylamine, diethylamine, Jtrimethylamine, triethylamine, -ethanolamine diethanolamine, Itriethanol amine, pyridine, N-methylpiperidine, n-propylamine, isopropylamine,butylamina -ethoxyethyl aminenetc., 'andtaking up the salt which forms in a suitable solvent, e. g. Water, methanol, ethanol, a mixtureof Water yand methanol or'a'mixture of water and Iethanol.

The basic dyes canbe added to the emulsions directly -or' in the form of a ysolution in a suitable solvent, e. g. methanol, or ethanol.

The pentamethine oxonol dyes and the basic dyes are advantageously added tothe Washed, finished emulsions and should be uniformly distributed throughout the emulsions.

'Our invention is directed primarily A'to the -customarily employed gelatino-silver-halide vdevel- @ping-*out emulsions, such as gelatin'o-silver-cliloride, 'gelatino'silverechlorobromide, gelatino-sils ver-iodochloride, gelatino-silver-chlorobromiodide, gelatino-silver-bromide and gel-atino-silverbromiodide emulsions.

Cyanine dyes, hemicyanine dyes and styryl dyes are defined in The Theory of the Photographic Process, C. E. Kennethv Mees, The MacMillan Company, New York, 1942. i

Emulsions prepared in accordance with our inventioncan be coated in the usual manner on any suitable support, such as glass, cellulose acetate iilm, cellulose nitrate film, polyvinyl acetal resin ifilm, paper or a suitable metal support.

3,3.-ethylenethiacyanine salts and 3,3'et'hyl ene-oxacyanine salts are described in the copending application of Leslie G. S. Brooker and Robert H. Sprague, Serial No. 563,086, filed November 11 ,1944, as are other N,Nethylenecyanine salts;

Pentamethine oxonol dyes can be prepared by condensing glutaconic aldehyde dianilide hydrochloride with one or more ketomethylene com-'- pounds selected from those represented by the following general formula: Y

n O= -H2 wherein Z represents the non-metallic atoms nec-` essary to complete a heterocyclic nucleus containing from to 6 Iatoms in the lieterocyclic ring, e. g. 3methyl1phenyl5pyrazo1one, 3-methyl- 1-sulfophenyl-5-pyrazolone, thiobarbituric acid, f

barbituric acid, etc. Two moles of the ketomethylene lcompound per mole of the glutaconic aldehyde dianilide hydrochloride are advantageously employed. The condensations are advantageously effected either in pyridine or in an ethyl alcoholic solution of a strong base such as triethylamine. The condensations can be accelerated by heating `on a water or steam bath.

What we claim as our invention and desire to be secured by Letters Patent of the United States V1. A photographic silver halide emulsion sen- -sitized with a supersensitizing combination of at least one oxonol dye selected from the group consisting of those represented by the following general formula: Y

zx ZQ wherein L represents a methine group and Z and Z' each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing. from 5 to 6 atoms in the heterocyclicring,

and the metal and ammonium salt forms of the` lformulated dyes, in a concentration of not more wherein L represents a methine group and Z and Z each represents the non-metallic atomsnecessary to complete a heterocyclic nucleus containing from 5 to 6 atoms inthe heterocyclic ring, and the. alkali Vmetal 'and ammonium' salt forms of the formulatedr dyes', inf afconcentration of not more than l0.25 gram per-.mole :of silver halide in the emulsion, and,-as a supersensitizer for the oxonol dye, at least one basic dyeselected from the group consisting of monomethine cyanine dyes, trimethine cyanine dyes, dimethine hernicyanine dyes and styryl dyes.

3. A photographic gelatino-silVer-halide developing-out emulsion sensitized with a supersensitizing combination of at least one oxonol dye selected from the group represented by the following general formula:

z\` ZR o:6 o:L-L:LL:L-=.:o:on f wherein L represents a methine group and Zand Z each represents the non-metallic atoms-necessary to complete a heterocyclic nucleus contain# ingfrom 5 to 6 atoms in the heterocyclic ring and the metal and ammonium salt forms ofthe vformulated dyes, ina concentration'of not-more than 0.25 gram per mole of silver' halide in the emulsion, and, as a supersensitizer for the oxonol dye, at least one 'basic dye selected'fromthe group consisting of monomethine cyanine dyes, trimethine cyanine dyes, dimethine hemicyanine `dyes and styryl dyes.

4. A photographic silver halide developing-out Vemulsion sensitized with a supers'ensitizin'g 'comi bination of at least one pentamethine oion'ol dye selected from the group represented bythe following general formula: Y

wherein Z and Z' each represents vthe nonmetallic atoms necessary to complete a heteroycyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring and containing a member selected from the group consisting of sulfo groups, carboxyl groups and the ammonium and alkali metal salt forms of said groups, in a concentration of not more than 0.25 gram yper mole of silver halide in the emulsion, and, asa super.-

sens'itizer for the pentamethine oxonol dye, atk

wherein Z and Z each represents the Anon; metallic atoms necessary to complete a hetero# cyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring and containing a member Aselected from the group consisting of sulfofgroups, carboxyl groups and the ammonium and alkali metal forms of said groups, in a concentration of not more than 0.25 gram per mole of silver halide in the emulsion. and, as a supersensitizer for the pentamethine oxonol dye, at least one basic dye selected from the group consisting of monomethine cyanine dyes, trimethine cyanine dyes, dimethine hemicyanine dyes and styryl dyes.

6. A photograph silver halide developing-out emulsion sensitized with a supersensitizing 'comf- -bination of at least one pyrazolone pentamethine -xonol dyeselectedfrom thefgroup representedby the following general formula:

IVIIZ"` f/Z\` o= c=oHcn=oHeH=cH b-OH wherein yZ .represents kthe .non-metallic 4atoms necessary to complete a 5-pyrazo1one nucleus containing a member selected from the group consisting of sulfo groups, carboxyl ,groups and the ammonium and alkali metal salt forms of said groups, in a concentration ofv not more.than.0.25 gram pen-moleof silver halide .inthe emulsion, and, as. a supersensitizer' for-the oxonol dye, at least one basic dye-selected from-the group consisting of monomethine cyanine dyes, vtri methine cyanine dyes, :dimethi-ne :hemicyaninc dyesand styryl'. dyes.

x7. -'A photographic gelatino-silver-halide developing-out` `emulsion sensitized with -a supersensi-tizing combination oat least one pyrazolone pentamethine oxonol dye selected from the group represented by the following general' formula.:

,2. o=--`o=oH-oH=cHcH=oH- wherein Z. yrepresents thehun-metallic atoms necessary to complete a -pyrazolone nucleus containing a member selected from the group consisting of sulfo groups, car-boxyl groups and the ammonium and alkali metal salt forms of saidfgroups, ina. concentration of `not more than 0.25. g-ramper mole of silver halide in thenemul.- sion, and', as a supersensiti'zer for the .oxonol/dye, at least one basic dye `selected from-:the group consisting vof monomethine cyanine dyes, trimethine cyam'ne dyes, dimethine hemic'yanine dyes and. styryl dyes.

v8. A photographie gelatina-silver-halide ide-- veloping-outv emulsion sensitized. with awsupersensitizing combination of at least one-penta methine floxonol dye selected from the group represented bythe following general formula:

/(Z\` ,IZI\` o==oH-CH=CH-CH=cH-=b-0H wherein Z and Z each represents the non-metal.1 lic atoms-necessary to complete a-heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, in a concentration .of not more than G25/gram per mole vof silver halidef in `the emulsion, and, as a supersensitizer for the oxonol dye, at least one monomethine cyanine dye which in and of itself confers no appreciable red sensitivity on the emulsion.

9. A photographic gelatine-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one pyrazolone pentamethine oxonol dye selected from the group represented by the following general formula:

wherein Z represents the non-metallic atoms necessary to complete a 5-pryazolone nucleus containing a member selected from the group consisting of carboxyl and sulfo groups and the ammonium and alkali metal salt forms of these groups, in a concentration of not more than 0.25 gram per mole of silver halide in the emulsion; and, as a supersensitizer for the oxonol dye, at least one monomethine cyanine dye which in and of itself confers no appreciable red sensitivity on the emulsion.

10. A photographic Igelantino-silver-halide developing-out emulsion sensitized with a superi0 sensiti'zing combination ofatleast one pyrazolone pentamethine oxonolclyel selected from the4 group represented by' the following general formula:

l,z'.\ y .z. o= e=cHCH=cHcH=oH c-on' whereinv Z `represents the non-metallic atoms necessary `to .complete a 5;-pyrazolone, :nucleus containing, a member selected from they group consisting of carboxyl. andy sulfov groups and. the ammonium and alkali metal salt forms of these groups, in `a concentration of not more than 0.25 gram per mole of silver halide in the emulsion, and, as a. supersensitizer for the oxonol dye, atleast one,` monomethine yNN.-ethylenecyanine dye. v

:1L-A photographic .gelatine-silver-halide..developing-out emulsionsensitized with ansupersensitizing-combination of at least onepyrazolone pentamethine -oxonol `dye selected from the group represen-tedby the following general formula;

/z'x l .z\

c-oir' wherein Z lrepresents the non-metallic ...atoms necessary to completea f-pyrazolone nucleus containingaa. member selected from the'. 4group consisting-of carboxyl and sulfo groupsandthe ammonium andalkaliy metal salt formsotthese groups,..in a concentration of noty more. than. 0.25 gram per mole of silver halide in the emulsion, and, as la supersensitizer for the oxonol dyegat least one monomethine.,3,3'ethy1enethiacyanine dye.

l2. A .photographic gelatinoesilverfhalide.de- Veloping-out emulsionsensitized with .a supersensitizing combination ofv atleast one pyrazolone pentamethine oxonol dye selected from the group represented by the following general formula:

.wherein -Z represents the non-metallic atoms .necessary to complete a fpyrazolone k'nucleus containing amember selected from' the group consisting of carboxyl andsulfo groups andthe ammonium .and `alkali metal. salt forms of these groups, ina concentration' of not more than 0.25 sgramnpermole .of silver halide inthe emulsion,

and, as a supersensitizer for the oxonolv dye; at least onemOnOmethine 3,3ethy1enethiacyani'ne Veloping-out emulsion sensitized with a supersensitizing combination of at least one pyrazolone pentamethine oxonol dye selected from the group represented by the following formula:

wherein Z represents the non-metallic atoms necessary to complete a 5-pyrazolone nucleus containing a member selected from the group consisting of carboxyl and sulfo groups and the ammonium and alkali metal salt forms of these groups, in a concentration of not more than 0.25 gram per mole of silver |halide in the emulsion,

and as a superse'nsitizer for the loxonol dye, at least one monomethine 3,'1diallqrlthia2'cya'` nine salt, in whichv the alkyl groups, are of the formula CdHzd-i-i wherein d representsa positive integer of from 1 to 2.

15. A photographic gelatine-silver-halide de` veloping-out vemulsion sensitized with a supersensitizing combination of at least one pyrazolone pentamethine oxonol dye selected from the group represented by the following formula:

:6 =CHCH=CH-oH=oH-=-0H wherein Z represents thenon-metallic atoms necessary to .complete a S-pyrazolone nucleus containing a member selected from the group consisting of carboxyl and sulfo groups and the ammonium and alkali metal salt forms of these groups, in a concentration of not more than 0.25 gram per mole of silver halide in the emulsion, and, as a supersensitizer, for the oxonol dye, at least one monomethine 3,1dia1kylthia2'cya nine halide, in which the alkyl groups are alkyl groups of the formula CdH2a+1 wherein d represents a positive integer ci from 1 to 2.

16V. A photographic .gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of bis l-p-sulfophenyll 3 methyl-5-pyrazolone-(4) l-pentamethine oxoi no1, in a concentration of from 0.043 to about 0.21

grani per mole of silver halide in the emulsion,

and, as a supersensitizer for the oxonol dye, 3 methyl- 1 -ethylthia-2' -fcyanine iodide.

17. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one pyrazolone pentamethine oxonol dye of the following formula: l

zox /zx` o= o=CHCH=CHCH=oHo o-OH wherein Z represents the non-metallic atoms necessary to complete a`5pyrazolone nucleus vcontaining a member selected from the group 'consisting of carboxyl and sulfo groups and the ammonium and alkali metal salt forms of these groups, in a concentration of notmore than 0.25

gram per mole of silver halide in the emulsion,

and, as a supersensitizer for the oxonol dye, at

least one 2- 1piperidyl) Vinyl] -benzothiazole alkyl salt in which the alkyl group is an alkyl sisting of carboxyland sulfo groups and the ammonium and alkali metal salt forms of these groups,'in aconeentration of not more than 0.25

gram per mole of silver halide in the emulsion, and, as a supersensitizer forY the-oxonol dye, at least one 2-[,8(1piperidyl)vnyll-benzothiazole alkyl halidein which the `alkyl group is an .alkyl group ofthe formula CdH2d+1 :wherein d represents a positive integer of from 1 to. 2. 1

19. A photographic .gelatino-silver-halide developing-lout emulsion sensitized with a supersensitizing combination of atleast one pyrazolone pentamethine oxonol dye of the following for-y mularf n ,l C=CH-CH=CH-CH%CH` o-oH wherein -Z represents the z non-metallic atoms necessary to complete i a -pyrazolone nucleus containing a member selected from the group consistingof carboxyland sulfo' groups and the ammonium and alkali metal salt .forms of these groups, in a concentration of notfmore than 0.25 gram per mole of silver halide inthe emulsion,

and, as a supersensitizer for the oxonol dye,

2-[-(1-piperidylvinyll benzothiazole methochloride.. f 1 y BURT H; CARROLL.

, REFERENCES CITED The following references are of record in the le of this patent;

juNiTED ySTATES PATENTS Number Name Date ,2,158,882V Mees f Mayie, 1939 Disclaimer 2,448,858. -Bfart H. Carroll and Cyril J. Staatl, Rochester, N. Y. OPTICALLY SUPER- SENSITIZED PHOTOGRAPHIC SILVER HALIDE EMULsIoN. Patent dated Sept.

7, 1948. Disclaimer led June 7, 1950, by the assignee, Eastman Kodak Company.

Hei'eby enters this disclaimer to claims 1 to 9, inclusive, and 14, 15, and 16 of said patent Without in any Way modifying the scope oi' aecting the validity of the remaining claims [ojaaz Gazette .my 11, 1950.] 

